FR2589325A1 - Dispersible granules based on substances which have a crop-protecting activity, and their preparation - Google Patents

Abstract

Dispersible granules based on substances which have a crop-protecting activity, characterised in that they comprise 35 to 98 % by weight of at least one substance which has a crop-protecting activity and 2 to 15 % by weight of a mixture of an alkali metal salt, or ammonium salt, of a condensate of naphtolsulphonate and resol and an alkali metal salt, or ammonium salt, of an alkylbenzenesulphonic acid.

Description

deleterious granules based on active substances
ohvtooharmaceutiaue and their method of reoaration
The invention relates to detrimental granules based on substances with plant protection activity.

 It also relates to a process for preparing these granules.

It is known to present the substances with plant protection activity, with a view to their implementation in the field, in the form of
- wettable powders used in suspension in water in the case of phytopharmaceutical substances which are insoluble in water and in solvents,
granules made by coating and gluing on an inert support,
- granules obtained by atomization of a highly concentrated suspension,
- granules obtained by compression-agglomeration,
liquid suspensions frequently referred to as "flowables".

 All these forms of presentation have disadvantages which will be recalled below.

 Wettable powders have the disadvantage of having fine particles in the form of dust, inconvenient for the user, a low density inducing bulky packaging and a character often mottant leading to the formation of hard blocks after prolonged storage under pressure.

 The coated-on granules are low-concentrated preparations and, moreover, generally undiluted in use.

 The manufacture of the atomized granules - which are obtained from slurries containing up to 70% of active substances, and therefore 30% of water, these slurries being dried by spraying at a high temperature in an atomizer - causes significant heat expenditure during the evaporation of the water from the slurry, which makes this process expensive; in addition, their low apparent density and the presence of fine particles (smaller than 100 microns) make these granules do not eliminate some of the disadvantages of wettable powders; this technique is illustrated by French Patent No. 2,030,315 in which microgranules are produced by spraying a suspension containing 30 to 60 parts of water on a rotating disc, mixed with a hot gas whose inlet temperature is between 180 and 270 ° C, the granules thus obtained having a diameter between only 75 and 400 microns.

 The tablet-agglomerated granules generally use large proportions of fillers and require the presence of binders, which greatly restricts their content of active ingredients; in addition, the conditions of realization and the nature of the charges of these tablets are essentially variable according to the active ingredients used and must be adjusted on a case by case basis; finally, the consistency and dispersibility in water of these granules are limiting factors; this technique is illustrated by French Patent No. 2,509,575, which describes the preparation of effervescent granules by mixing chloro-2- (trifluoromethyl) -4-phenoxy-5-nitrobenzoate (acifluorfen) acid with sodium carbonate or bicarbonate and with aluminum stearate; a major disadvantage of this method is that the choice of carbonate is related to the acidic nature of the active ingredient and that the process is not generalizable to all bioactive substances.

 Finally, the liquid suspensions called "flowableus" - which are obtained by incorporating into a liquid phase, aqueous or solvent, the active materials in the solid state and, if possible, in the form of powders as well as the formulation additives, the The slurry thus obtained is milled in a wet bead mill to the desired particle size and the resulting slurry, optionally thickened in a conventional manner to retard sedimentation of the solid grains in the liquid phase, very often has a limited stability over time. the heat tending to fluidify them, to increase the sedimentation and thus to favor hard deposits at the bottom of the container, these suspensions are therefore applicable only to the solubility active substances in the carrier liquid of less than a few hundred ppm; active substances with a change of state within a temperature range of -10 ° C to + 80 ° C are difficult to present according to such formulations.

The object of the invention is, above all, to overcome the drawbacks of the prior art and to provide deleterious granules based on substances with plant protection activity.
- the concentration of active substances of which may be as great as possible and, in any event, greater than 35% (the charges limiting this content generally have the advantage of aiding cohesion, hardness and the dispersion of the granule in the water, and consequently the possibilities of decreasing the proportion of these charges are generally very limited).

- the particle size is as homogeneous as possible and the rate of fine particles as small as possible so that the resulting granules do not sense the disadvantages of soiling, re-emergence and possible toxicity that we encounter in the handling of powders,
- which flow freely on each other when poured,
- the preparation of which can be obtained with the least possible energy, the proportion of granulation water to be evaporated being the lowest possible,
- Of which the hardness is sufficient to allow them to not crash when they are subjected to significant pressures for prolonged storage, a feature which is often in opposition to the desired spontaneity of disintegration when the granule is introduced into the water , at the time of application, because the hard granules tend not to fall apart,
- whose spontaneity of the disintegration allows a fine and homogeneous division in the water in the shortest time and with the least possible mechanical means possible (these granules, said self-delitable, leading to particles after disintegration whose dimensions are those divided solids before granulation),
- whose disintegration in water leads to a slurry whose suspensivity is sufficient so that it is as homogeneous at the end of application as at the beginning, and this even when the agitation is reduced (a fundamental characteristic because the application aqueous preparations being carried out by displacement of the spreading device in the field, it would be unimportant to spread solutions of variable concentration of active material from one place to another of the place of application, a poor suspensivity that could cause otherwise a physical agglomeration at the bottom of the application tank capable of blocking the spreading device),
- whose stability over time is such that all of their physical properties are preserved after 14 days of storage at +54 ° C or after 2 years of storage at room temperature.

However, the Applicant Company has had the merit of finding that it was possible to prepare granules based on all substances with plant protection activity that have all the advantages mentioned above by incorporating into the preparation of the substances to be granulated. on the one hand a dispersing binder consisting of an alkaline or ammonium salt of a condensate of naphtholsulfonate and resol and, on the other hand, a disintegrating hydrotrope consisting of an alkaline salt or ammonium salt of an alkylbenzenesulfonic acid. the granules thus formed having both a hard dry character, a high speed of disintegration and good suspensivite during the application in suspension in water,
Therefore, the detrimental granules based on substances with phytopharmaceutical activity in accordance with the invention are characterized in that they comprise from 35 to 98% by weight of at least one substance with plant protection activity and from 2 to 15% by weight. by weight of a mixture of alkali metal salt or ammonium salt of a condensate of naphtholsulfonate and resol and alkali or ammonium salt of an alkylbenzenesulphonic acid.

 Phytopharmaceutical substances that are relevant include herbicides, insecticides, acaricides, fungicides, nematicides, rodenticides, growth promoters, and many of these substances, which provide complementary or different activities, may be included in the composition. of one and the same granule.

 In addition to the active ingredient comprising the substance (s) with phytopharmaceutical activity, the dispersant binder and the disintegrating hydrotrope, the granules according to the invention may contain up to 50% of additives such as wetting agents and secondary dispersants, inert fillers and optionally auxiliary products such as dyes, perfumes, defoamers, agents for protecting active ingredients, agents providing a delay effect, all these products being of a nature to favor the characterization of the product, its activity, its use or bringing to a marketable title of the corresponding granules.

 More particularly, they may contain from 0.1 to 5% by weight, preferably from 0.2 to 1% by weight. a wetting agent and a secondary dispersant.

This being,
the above condensate is a condensate of s-naphtholsulphonate and resol having a molar ratio "s-naphtholsulfonate / resol" of between 0.5 and 2 and preferably. between 0.8 and 1.25,
the alkylbenzene radical of the aforesaid alkaline or ammonium salt of alkylbenzenesulphonic acid comprises one or more short branched or unbranched alkyl chains of 1 to 3 carbon atoms, preferably two isopropyl or methyl chains.

 For the preparation of naphtholsulfonate. mono-naphtholsulfonic acid or Schaeffer acid is used which is obtained by hot sulfonating the naphthol with 93-98 Z sulfuric acid.

It is also known that the resols are products of the condensation of formaldehyde with phenols (phenol, cresol, under the influence of the alkalis, and it may be useful to refer to this subject in "Chemistry of Paints".
Varnish and Pigments "Volume 1, pp. 303-356 by G. Champetier, H. Rabaté, JL Rabate, Dunod, 1956.

 The condensation between the naphtholsulfonate and the resol is carried out via the methylol groups present in the resol at temperatures of about 100 for 8 hours. (Always see the book "Chemistry of Paints, Varnish and Pigments * identified above).

 The dialkylbenzenesulfonic acid is obtained by conventional sulfonation of a mixture of commercially available ortho, meta, para, dialkylbenzene isomers (for example, by 80-100 'sulfonation with a mixture of 98% sulfuric acid). and oleum).

 The weight ratio "binder-dispersant / hydrotrope-disintegrant" is between 0.5 and 20 and preferably between 1 and 10.

 The preparation process according to the invention, granules according to the invention, is characterized in that an intimate mixture, at the desired doses, of the active ingredient (s), the dispersant binder and the hydrotrope is produced. disintegrant and optionally other adjuvants, in the form of a homogeneous fine powder which can optionally be subsequently milled on a powder mill before rehomogenization, this powder then being introduced into a granulation apparatus. in particular a rotating plate granulator or a tank provided with agitators and clod-breaking systems, the granules finally being dried.

 As an example of such a device, it is reported that manufactured in France at the GUEDU Company; in this apparatus, water is sprayed with stirring onto the powder until granules of the desired size appear; the amount of water poured is adjusted according to the composition to be granulated and varies from 3 to 30% of the weight of the powder to be granulated.

 According to a variant of the aforesaid process, a powder to be granulated is prepared which contains only a part of the "binder-dispersant / hydrotrope disintegrating" mixture and adjuvants and this powder is sprayed with an aqueous solution comprising the balance of the binder-dispersant / hydrotrope mixture. disintegrant and adjuvants, the granules obtained being then dried.

 By way of example, it is possible to introduce into the powder 50 Z all of the mixture "binder-dispersant / hydrotropic disintegrant" or to introduce only certain constituents of the "disintegrating binder-dispersanthydrotropic" mixture or to introduce only the dry constituents of the disintegrating hydrotrope-dispersing / blending mixture, the composition being incorporated at the correct dose into the spray water, this aqueous solution possibly being able to be sprayed while hot.

 For the drying of the granules, it is possible to use either a granulation tank equipped with a heating and / or evacuation device, or a hot air tunnel separated from the granulation site, or with an infrared radiation. either a passage in a fluidized bed, or a combination of two or more of these means.

 The drying device is chosen not only according to its cost but also taking into account the thermal stability, the melting point, or the compatibility of the active substances used.

 Under normal conditions, a drying time of drying is chosen between 30 and 100 ° C. and preferably between 35 and 95 ° C. In the case where the drying is at least partially ensured by a vacuum, the temperature may be between 0'C and 60'C.

 The granules obtained still contain between 0.1 and 3% and preferably less than 1% of water.

These granules will eventually be sieved in order to quantitatively obtain the desired particle size fraction; the non-standard granules after grinding can be recycled into the starting powder,
The granulometry of the granules can be adjusted between 50 microns and 1 cm and preferably between 100 and 1400 microns to be compatible with the standards of microgranules dry spreading.

 In the following examples, which are in no way limiting and which illustrate advantageous embodiments of the invention. the characteristics of the granules are specified and possibly determined as follows.

 The composition of the preparation powders as well as the quantity of water chosen for the granulation are given in grams for about 100 grams of powder ready for graveling, the amount of waste water can be given as a weight percentage of the granule ready for use. use, it is measured by stoving at 5 ° C of 100 g of granules to constant weight.

The disintegration is appreciated by pouring a weight P equal to 1 g of granules in a test tube filled with 250 ml of hard water (according to the Collaborative International Pesticide
CIPAC Analytical Council MT 18.1.4). Five rounds of the specimen are immediately made and the suspension is then poured onto a 40 micron sieve. The sieve refusal is roughly rinsed, then poured with the rinse water into a calibrated cup (T in g). The whole is dried in an oven until constant weight (T 'in g ?.

The percentage of disintegration is calculated by the formula
P - (T '- T)
Disintegration (%) = 100 x
P
The disintegration must be at least 80% for an acceptable granule.

 The suspensivity is evaluated according to the principle of the CIPAC MT 15.1 method arranged in the manner indicated below. A mass P = 10 g of granules is poured directly into a rodee test tube of 1 liter filled with 1 liter of hard water (CIPAC MT 18.1.4); 15 complete reversals of the closed specimen are made; this is left for 30 minutes without agitation at 20 ° C. and at the end of this time. 9/10 of the suspension is removed by suction as specified in the method; the remainder is placed in an oven-calibrated beaker at 105 ° C to remove the water to constant weight. or P '(in g) being the weight of residue thus obtained.

The percentage of suspensivity is given by the formula
Suspensivity (%) = ## x #### x 100
The suspensivity must be at least 60% for an acceptable granule.

 The wettability is assessed according to the principle of CIPAC method MT 53.3.1 arranged as it will be in diqué.

 A mass of 1 g of granules is poured into a 250 ml beaker filled with 200 ml of hard water (CIPAC MT 18.1.4), the time required to completely wet the mass is timed as specified in the method.

 Hardness is appreciated empirically, by pouring some granules into the palm of the hand and trying to crush them with the index finger of the opposite hand.

To do this, press with the finger by exerting a slight rotational movement thereof. The granules which, subjected to pressure and attrition by mutual friction, produce dust, are said to be tender; if they do not produce dust after about 5 seconds of experimentation, they are declared hard.

 To evaluate the particle size, a mass P of about 50 g of granules is passed over a stack of two ASTM 11.70 sieves having an opening of 1400 and 106 microns, respectively. After screening for 30 minutes, a mass P 'having passed the 1400 micron sieve and retained on the 106 micron sieve is collected.

The percentage of granules having the desired granulometry is expressed by the formula
P '
particle size 106 - 1400 (Z) = px 100
In the examples which follow, a naphtholsulfonate and resol condensate is used, in a nonlimiting manner, in which the molar ratio "s-naphtholsulphonate / resol" is equal to 1.

 The resol forming this condensate is prepared by reacting 1 mole of cresol and 2.5 moles of formaldehyde in the presence of sodium hydroxide, as described in the book "Chemistry of Paints, Varnish and Pigment", identified above.

 The condensate is in the form of an atomized brown powder whose residual moisture is less than 5%; in the examples, this product is referred to as "condensate".

 In the examples which follow, sodium bis-diisopropylbenzene sulphonate, which is available in two forms, namely a 40% aqueous solution of dry extract, a white atomised powder with a residual moisture content of 1%, is used as alkylbenzene sulphonate. .

EXAMPLE 1
A herbicidal formulation is prepared by mixing 90 g of standard industrial grade atrazine (or 2-chloro-ethylamino-4-isopropylamino-6-s-triazine) (å 97% purity), 7 g of condensate, 1.8 g of powdered diisopropylbenzenesulfonate, 0.6 g of sodium lignosulfonate and 0.2 g of sodium dibutylnaphthalenesulphonate until perfect homogeneity.

 The whole is milled in a laboratory mill to obtain a powder of average particle size centered on 5 microns, then placed on a rotating laboratory type granulator Eirich type rotated on which is effectively sprayed 26 g of water . The granules thus obtained are then dried in a heating cabinet set at 80 ° C. for 3 hours. This produces freely flowable and easily flowable granules. Residual moisture is 0.5% by weight and contains about 87% herbicide atrazine.

In order to illustrate the advantages provided by the invention, the characteristics of the granules obtained with the formulation of Example 1 are compared in Table I with the characteristics of the granules obtained with eight formulations A, B, C, D, respectively. , E, F, G, H of the prior art based on atrazine, these formulations having the following composition
Formulation A
- Atrazine ..................................... 90%
- Nekal BX Sec (sodium alkylnaphthalenesulphonate marketed by the company BASF? ..... 3. '.

Tamol NNO {sodium polynaphthalene sulfonate
marketed by the company BASFB, 7 Z
Formulation B
- Atrazine 0 90 Z
- Nekal BX Sec .................................. 3%
- Sodium lignosulfonate ...................... 7 X
Formulation C
- Atrazine, 90 Z - Nekal BX Sec .................................. 3 X
- Calcium lignosulfonate ..................... 7%
Formulation D
- Atrazine ...................................... 90 Z
- Nansa HS / 80.S {laurylbenzene sulfonate
sodium marketed by the company MARCHON .... 3 X
- Sodium lignosulfonate ....................... 7 Z
Formulation E
- Atrazine ...................................... 90 Z
- Nekal BX Sec. :: 3 Z
- Tamol NNO ..................................... 6,5Z
- Klucel 'H (marketed hydroxypropylcellulose
by the company HERCULES) ...................... 0,5Z
Formulation F
- Atrazine ....................................... 90 Z
- Cemulsol NP 10 {nonylphenol with 10 groups
ethylene oxide marketed by the Company
RHONE POULENC) ................................. 2%
- Tamol NNO ...................................... 8%
Formulation G
- Atrazine ....................................... 90 Z
- OT 75 Aerosol (sodium dioctyl sulfosuccinate)
sold by AMERICAN CYANAMID) 2 Z
- Tamol NNO ...................................... 8 Z
Formulation H
- Atrazine, 90%
- Nekal BX dry, 3 3 Z
- Orotan 731 SD (sodium salt of an acid
polycarboxylic marketed by the Company
ROHM & HAAS) ..................................... 7% TABLE

Crushing <SEP> Suspensivity <SEP> Wettability <SEP> hardness <SEP> Grading <SEP> Observations
<tb> (%) <SEP> (%) <SEP> (seconds) <SEP> (%)
<tb> Example <SEP> 1 <SEP> 99.5 <SEP> 95.8 <SEP> 60 <SEP> hard <SEP> 90 <SEP> granulate <SEP> fluent
<tb> Formulation <SEP> A <SEP> 98.8 <SEP> 96.8 <SEP> 60 <SEP> soft <SEP> 87 <SEP> granulate <SEP> fluent
<tb> formulation <SEP> B <SEP> 99.4 <SEP> 96.3 <SEP> 75 <SEP> soft <SEP> 81 <SEP> granulate <SEP> fluent <SEP> but <SEP> tacky
<tb> on <SEP> the <SEP> walls <SEP> of the <SEP> container
<tb> Formulation <SEP> C <SEP> 86.7 <SEP> 79 <SEP> 20 <SEP> soft <SEP> 79.8 <SEP> granulate <SEP> fluent <SEP> but <SEP> tacky
<tb> on <SEP> the <SEP> walls <SEP> of the <SEP> container
<tb> Formulation <SEP> D <SEP> 96.5 <SEP> 55 <SEP> 15 <SEP> soft <SEP> 95.3 <SEP> granulate <SEP> fluent <SEP> slightly
<tb> sticky <SEP> on <SEP> the <SEP> walls <SEP> of
<tb> container
<tb> Formulation <SEP> E <SEP> 97.7 <SEP> 29 <SEP> 75 <SEP> hard <SEP> 86.6 <SEP> granulate <SEP> fluent
<tb> formulation <SEP> F <SEP> 50.1 <SEP> 43.5 <SEP> 15 <SEP> hard <SEP> 76 <SEP> granulate <SEP> fluent
<tb> (blocks)
<tb> formulation <SEP> G <SEP> 78.1 <SEP> 15.1 <SEP> 20 <SEP> soft <SEP> 94.8 <SEP> granulate <SEP> fluent
<tb> Formulation <SEP> H <SEP> 98.5 <SEP> 96.1 <SEP> 45 <SEP> soft <SEP> 95.1 <SEP> granulate <SEP> fluent <SEP> but <SEP> tacky
<tb> on <SEP> the <SEP> walls <SEP> of the <SEP> container
<Tb>
The superiority of the granules according to the invention, whose characteristics are otherwise unchanged after 14 days of storage at a temperature of + 54 ° C., is clearly apparent from the examination of the figures and observations compiled in Table I.

EXAMPLES 2 to 21
In each of these examples, the active ingredient (s) is (are) formulated with appropriate amounts of condensate, sodium diisopropylbenzene sulphonate, sodium lignosulfonate. sodium dibutylnaphthalene sulphonate and, when mentioned, kaolin clay to produce about 100 g of powder. This powder is milled in a laboratory powder mill to obtain a fine powder of average particle size centered on 5 microns. It is then placed on an Eirich-type laboratory tray granulator rotated and a variable amount of variable water for each example is sprayed onto the powder.

 The granules thus obtained are then dried under the conditions specified for each example. 100 g of free-flowing and easily flowable granules are thus obtained.

 The residual moisture as well as the contents of phytopharmaceutical activity materials are specified for each example.

 These granules can be subsequently sieved to retain only the particle size cut 106-1400 microns before packaging.

 The pellets having been stored for 14 days. at +54 C on the one hand and for 2 years at room temperature on the other hand, have characteristics of use unchanged compared to those mentioned for each example.

EXAMPLE 2
Autodelatable granules titrating 85% bromoxynil were prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate,. 1.8 g
. Condensate .................................... 7 g
. Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Technical Bromoxynil with 94% purity ........ 90 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 11.59.

 The granules are dried for 3 hours in a ventilated oven and set at 80 C.

 The amount of waste water after drying in the ready-to-use granules is 0.4 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 gil for 30 mni 86 Z
- Disintegration (out of 1 g, 5 immediate turnarounds) 99%
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness {finger assessment) very hard
- Granulometry particle size cut
106-1400 μm) 90Z.

EXAMPLE 3
Autodelatable granules titrating 85% of ioxynil are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
. Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate 0.2 g
. Technical Ioxynil with 9% purity ........... 90 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 159.

 The granules are dried for 3 hours in a ventilated oven and set at 80 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 0.4 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 g / l for 30 minutes) 65 Z
- Disintegration (on I g, 5 immediate turnarounds) 84 Z
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 pm) 90 t.

EXAMPLE 4
Autodeletable Z-titrants of ioxynil as the butyric ester and 60% of 2,4-MCPP as the sodium salt are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ......... 2.1 g
. Condensate ..................................... 3.5 g
. Sodium lignosulfonate; 0.7 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
Kaolinic clay ............................ 0.2 g
. Ioxynil butyrate at 77.3 Z equivalent
of ioxynil .................................... 19.4 g
2,4-HCPP, sodium salt 81.8%
of equivalent acid ........................... 73.4 g
The quantity of water used and absorbed during granulation for 100 g of powder to be granulated is 6 g
The granules are dried for 4 hours in a ventilated oven and set at 50 ° C.

The quantity of residual water after drying in the granules ready for use is 0.5 g per 100 g,
The characteristics of the granules thus obtained are as follows:
- Suspensivity on 10 g / l for 30 minutes) 93 Z
- Disintegration (on tg, 5 immediate turnarounds) 100 X
- Wettability (over 1 g, wetting time
complete) 10 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 pm) 80 Z
EXAMPLE 5
Autodeletable granules titrating 4% of ioxynil as butyric ester, 13% of 2,4-MCPP in the form of sodium salt and 23% of isoproturon are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate .O. * 1.8 g
. Condensate .................................... 7 g
. Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Kaolin clay ............................ 45.6 g
. Ioxynil butyrate at 77.3 Z equivalent
of ioxynil .................................... 5.2 g
2,4-MCPP, 81,8 Z sodium salt
of acid equivalent ........................... 15.9 g. Technical isoproturon at 98.8 Z purity .. 23.3 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 9 g.

 The granules are dried for 4 hours in a ventilated oven and set at 50 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 0.4 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity <on 10 g / l for 30 minutes) 83%
- Disintegration (on 1 g, 5 immediate reversals? 100 Z
- Wettability (over 1 g, wetting time
complete 5 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 pm1 90%.

example6
Autodelatable granules containing 7.5% bromoxynil, 7.5% ioxynil as butyric ester and 60% 2,4-MCPP as the sodium salt are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 2.1 g
. Condensate .................................... 3,5 g
. Sodium lignosulfonate ..................... 0.7 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Kaolinic clay ............................ 1.9 g
. Technical Bromoxynil 94 Z .................. 8 g
. Ioxynil butyrate at 77.3 Z equivalent
of ioxynil ....................................... 9.7 g
. 2,4-MCPP, 81,8 Z sodium salt
of equivalent acid ........................... 73.4 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 6 g.

 The granules are dried for 4 hours in a ventilated oven and set at 50 C.

 The quantity of residual water after drying in the ready-to-use granules is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivite (on 10 g / l during 30 mn) 96 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 100 Z
- Wettability (over 1 g, wetting time
complete) 5 sec
- Hardness (hard finger assessment
- Granulometry (particle size cut
106-1400 pm) 85Z.

EXAMPLE 7
Autodelatable granules of 8% bromoxynil, 24% 2-MCPP as the sodium salt and 48% chlortoluron were prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
Condensate 7 7 g
Sodium lignosulfonate, 0.6 g
. Sodium dibutylnaphthalenesulfonate 0.2 g
Kaolinic clay, 1.8 g
2,4-MCPP, sodium salt 81.8 X
of acid equivalent ........................... 29.4 g
Technical Bromoxynil, at 94 X purity ....... 8.5 g
. Technical Chlortoluron with 96% purity e 50 g
The amount of water used and aborbed during granulation for 100 g of powder to be granulated is 6 g.

 The granules are dried for 4 hours in a ventilated oven and set at 50 C.

 The quantity of residual water after drying in the ready-to-use granules is 0.7 g per 100 g.

The characteristics of the granules thus obtained
are the following
- Suspensivity (on 10 g / l during 30 mn) 74%
- Disintegration (on 1 g, 5 immediate turnarounds) 99.5%
- Wettability (over 1 g, wetting time
complete), 5 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 m) 80%.

EXAMPLE 8
Autodeletable granules titrating 21% of biomoxynil, 50% of 2,4-MCPP in the form of
sodium and 7% terbuthylazine.

For this purpose, the granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 5 g
Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Kaplinic clay ............................ 0.4 g
2,4-MCPP, 81,8 Z sodium salt
of equivalent acid ........................... 61.2 g
. Bromoxynil technique. at 94 X purity ....... 22.3 g
. Technical Terbuthylazine 99% pure, 7.1 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 4 g.

 The granules are dried for 4 hours in a ventilated oven and set at 50 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 1 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 g / l for 30 minutes) 89 Z
- Disintegration {on 1 g, 5 immediate turnarounds) 100 Z
- Wettability (over 1 g, wetting time
complete) 5 sec
- Hardness (hard finger assessment
- Granulometry particle size cut
106-1400 pm) 95%.

EXAMPLE 9
Autodelatable granules titrating 92% of aminotriazole are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 0.7 g
. Condensate .................................... 2.8 g
. Sodium lignosulfonate ..................... 0.2 g
. Sodium dibutylnaphthalenesulfonate ......... 0.1 g
. Technical aminotriazole, 96% purity ... 96 g
The quantity of water used and absorbed during granulation for 100 g of powder to be granulated is 6 g
The granules are dried for 1 hour in a vacuum oven of 20 mm of mercury and set at 50 ° C.
The amount of wastewater after drying in the ready-to-use granules is 0.2 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 gll for 30 minutes) 100 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 100 Z
- Wettability (over 1 g, wetting time
full? immediate
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 μm) 90%.

 Milling: a mass of 50 g of granules subjected for 100 hours at a pressure of 50 g / cm 2 at 54 ° C. remains flowable at the end of the test, whereas the same test carried out on untreated and powdered aminotriazole gives a single block entirely motte.

EXAMPLE 10
Autodeletable granules titrating 41.5% aminotriazole, 33% diuron and 11.5% bromacil were prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
Sodium lignosulfonate ..................... 0.6 9
. Sodium dibutylnaphthalenesulfonate, 0.2 g
Technical aminotriazole with 96% purity ..... 43,2 9
. Technical Diuron with 95% purity ............ 34.6 g
. Technical Bromacil, 95% purity ......... 12.2 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 109.

 The granules are dried for 3 hours in a ventilated oven and set at 800C.

 The quantity of residual water after drying in the ready-to-use granules is 0.4 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn) 80 Z
- Disintegration (on 1 g, 5 immediate reversals 95 Z
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 μm) 90Z.

EXAMPLE 11
Autodelatable granules of 75% aminotriazole and 10% sodium thiocyanate were prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. 94 Z sodium thiocyanate
of purity .................................... 10.6 g
Technical aminotriazole with 96% purity ..... 78.1 g
Kaolinic clay ............................ 1.2 g
The quantity of water used and absorbed during the granulation for 100 g of powder to be granulated is T g.

 The granules are dried for 45 minutes in a rotary drier at 150 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows
- Suspensivity (on 10 g / l during 30 mn? 100 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 100 Z
- Wettability (over 1 g, wetting time
full? 5 sec
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 μm) 90Z.

EXAMPLE 12
Autodeletable granules titrating 33% of aminotriazole and 37% of trichloroacetic acid are prepared. in the form of sodium salt and 5% 2,4-MCPA, in the form of sodium salt.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diispropylbenzenesulfonate ........ 1.8 g
. Condensate 0 7 g
Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Kaolin clay ............................ 4 g
Technical aminotriazole with 96% purity ..... 34.4 g
. 83.6% sodium trichloroacetic acid
of equivalent acid ........................... 44.3 g
. 2,4-MCPA, sodium salt at 75% equivalent
acid ........................................ 6.7 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 6.59.

 The granules are dried for 4 hours in a ventilated oven and set at 40 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 1 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn) 100 Z
- Disintegration (on 1 g, 5 immediate reversals 100 Z.

- Wettability (over 1 g, wetting time
complete) immediately
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 m) 95%.

EXAMPLE 13
Autodelatable pellets of 40% aminotriazole and 40% ethidimuron are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
Sodium diisopropylbenzenesulfonate, 1.8 g
. Condensate ....................................... 7 g
Sodium lignosulfonate ..................... O, E g
. Sodium dibutylnaphthalenesulfonate - 0.2 g
. Kaolinic Clay 6.1 g
. Technical aminotriazole with 96% purity ..... 41.7 g
- Technical Ethidimuron at 95% purity, 42.1 g
The amount of water used and absorbed during granulation per 100 g of powder to be granulated is 7.59 *
The granules are dried for 3 hours in a ventilated oven and set at 80 C.

 The quantity of residual water after drying in the ready-to-use granules is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 g / l for 30 minutes) 85 X
- Disintegration (out of 1 g 5 immediate turns) 99 Z
- Wettability (over 1 g, wetting time
complete) 5 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400Mm) 90Z.

EXAMPLE 14
Autodegradable granules titrating 64% of aminotriazole and 16% of picloram in the form of potassium salt are prepared.

To do this, granulation is subjected to a powder whose composition is as follows:
. Sodium diisopropylbenzenesulfonate .e 0.9 g
. Condensate .................................... 3,5 g
Sodium lignosulfonate, 0.3 g
. Sodium dibutylnaphthalenesulfonate ......... 0.1 g
. Kaolinic clay ............................ 9.3 g
Technical aminotriazole with 96% purity ..... 66.7 g
. Picloram. potassium salt, 86 Z
of acid equivalent ............................. 18.6 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 8.59.

 The granules are dried for 3 hours in a ventilated oven and adjusted to BOC.

 The quantity of residual water after drying in the ready-to-use granules is 0.6 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 g / l for 30 minutes) 93%
- Disintegration (on 1 g, 5 immediate turnarounds) 99 Z
- Wettability (over 1 g, wetting time
complete) 5 sec
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 μm) 90Z.

EXAMPLE 15
27% of aminotriazole, 9% of karbutylate [N- (3,3-dimethyl-ureido) -phenyl-tert.butyl carbamate], 27% of atrazine and 18% of diuron were prepared as autodelitable granules.

To do this, granulation is subjected to a powder whose composition is as follows. Sodium diisopropylbenzenesulfonate d 1, 1, S g
. Condensate, 7 g
. Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Kaolinic clay ............................ 5.3 g
. Technical aminotriazole with 96% purity. . . 28.1 g
. Technical Atrazine with 97% purity .......... 27,8 9
. Technical Diuron with 95% purity ............ 18.9 g
. Technical 95 kt Karbutylate of purity ....... 9.5 g
The quantity of water used and absorbed during the granulation for 100 g of powder to be granulated is 14 g.

 The granules are dried with stirring for 3 hours in a ventilated cabinet and set at 80 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 0.8 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 g / l for 30 minutes) 70 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 84 Z
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness (finger assessment) very hard
- Granulometry (particle size cut
106-1400 μm) 80Z.

EXAMPLE 16
87 Z autodeletable granules of simazine are prepared.

To do this, granulation is subjected to a powder whose composition is as follows:
. Sodium diisopropylbenzenesulfonate ........ 1.8 g. Condensate 7 g
Sodium lignosulfonate ..................... 0.6 9
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
. Technical simazine with 97% purity .......... 89.7 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 199.

 The granules are dried for 3 hours in a ventilated oven and set at 80 ° C.

 The quantity of residual water after drying in the ready-to-use granules is 0.3 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn: 90 Z
- Disintegration (on I g, 5 immediate turnarounds) 99 Z
- Wettability (over 1 g;
complete) 60 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 μm) 90Z.

EXAMPLE 17
Autodelatable granules containing 79% folpel are prepared.

To do this, granulation is subjected to a powder whose composition is as follows:
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate o 0.2 g Kaolinic clay. . 2.1 g
. Technical Folpel with 90% purity. 87.8 9
The quantity of water used and absorbed during the granulation for 100 g of powder to be granulated is
The granules are dried for 2 hours in a ventilated oven and set at 80 C.

 The quantity of residual water after drying in the ready-to-use granules is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivite (on 10 g / l during 30 mn) 80 Z
- Disintegration (on d, 5 immediate turnarounds) 99%
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 m) 80 Z
EXAMPLE 18
Autodeletable granules titrating 81% captan are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
Sodium lignosulfonate ..................... 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
Kaolinic clay ............................ 2.2 g
Technical Captane with 92% purity ........... 88 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 139.

 The granules are dried for 2 hours in a ventilated oven and set at BO'C.

 The amount of wastewater after drying in the ready-to-use granules is 0.2 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn) 80 Z
- Disintegration (out of 1 g, 5 immediate reversals) 99 2
- Wettability (over 1 g, wetting time
complete) 30 sec
- Hardness (hard finger assessment)
- Granulometry (granulometric cut
106-1400 m) 95 2.

EXAMPLE 19
Autodelatable granules titrating 85% of captafol are prepared.

To do this, granulation is subjected to a powder whose composition is as follows:
. Sodium diisopropylbenzenesulphonate., 1.8 g Condensate T 7 7 g
Sodium lignosulfonate 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
Kaolin clay ............................ 2.3 g
. Technical Captafol with 97% purity .......... 87.6 s
The quantity of water used and absorbed during the granulation for 100 g of powder to be granulated is 15 g.

 The granules are dried for 2 hours in a ventilated oven and set at 80 C.

 The quantity of residual water after drying in the granules ready for use is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn) 85%
- Disintegration (on 1 g, 5 immediate turnarounds) 99 X
- Wettability (over 1 g, wetting time
complete) 45 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 μm) 90Z.

EXAMPLE 20
Autodelatable granules titrating 81% sulfur are prepared.

To do this, granulation is subjected to a powder whose composition is as follows. Sodium Diisopropylbenzenesulfonate .... 0 ... 1.8 g
. Condensate .................................... 7 g Sodium lignosulfonate ........ ........ 0.6 g
. Sodium dibutylnaphthalenesulfonate ......... 0.2 g
Kaolinic clay ............................ eg
. Sulfur ....................................... 81 g
The amount of water used and absorbed during the granulation per 100 g of powder to be granulated is 199.

 The granules are dried for 4 hours in a thin layer in a ventilated oven and set at 50 C.

 The quantity of residual water after drying in the ready-to-use granules is 1 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (over 10 gil for 30 minutes) 77 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 94 Z
- Wettability (over 1 g, wetting time
complete) 60 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 pm) 85Z.

EXAMPLE 21
Autodeletable granules titrating 85% of diuron are prepared.

To do this, granulation is subjected to a powder whose composition is as follows
. Sodium diisopropylbenzenesulfonate ........ 1.8 g
. Condensate .................................... 7 g
Sodium lignosulfonate ..................... 0.6 g
Sodium dibutylnaphthalenesulfonate ......... 0.2 g
Technical diuron with 95% purity ............ 89.5 g
The quantity of water used and absorbed during the granulation for 100 g of powder to be granulated is 22 g.

 The granules are dried for 2 hours in a ventilated cabinet and set at 80 C.

 The quantity of residual water after drying in the ready-to-use granules is 0.5 g per 100 g.

The characteristics of the granules thus obtained are as follows:
- Suspensivity (on 10 g / l during 30 mn) 60 Z
- Disintegration (on 1 g, 5 immediate turnarounds) 90 Z
- Wettability (over 1 g, wetting time
complete) 60 sec
- Hardness (hard finger assessment)
- Granulometry (particle size cut
106-1400 μm) 90Z.

 As a result of which and whatever the embodiment adopted, delusable granules are thus available whose characteristics and advantages result sufficiently from the foregoing so that it is unnecessary to insist more on this subject.

 It goes without saying and as it follows already from the foregoing, the invention is not limited to those of its modes of application and of realization which have been more especially envisaged; it embraces, on the contrary, all variants.

Claims (7)

 1. Crumbly granules based on substances having plant protection activity, characterized in that they comprise from 35 to 98% by weight of at least one substance with plant protection activity and from 2 to 15% by weight of an alkaline salt mixture. or ammonium of a condensate of naphtholsulfonate and resol and alkali or ammonium salt of an alkylbenzenesulfonic acid.  2. Granules according to claim 1, characterized in that the weight ratio "binder-dispersant / hydrotrope-disintegrant" is between 0.5 and 20 and preferably between 1 and 10.  3. Granules according to one of claims 1 and 2, characterized in that one takes of ss-naphtholsulfonate and a molar ratio "naphtholsul'onate / resol" between 0.5 and 2 and preferably between 0.8 and 1.25.  4. Granules according to one of claims 1 to 3, characterized in that the alkylbenzene radical of the aforesaid alkali metal or ammonium salt of alkylbenzenesulfonic acid comprises one or more short branched or unbranched alkyl chains of 1 to 3 atoms. carbon, preferably two isopropyl or methyl chains.  5. Granules according to one of claims 1 to 4, characterized in that they contain up to 50% of additives such as wetting agents and secondary dispersants, inert fillers and optionally auxiliary products such as dyes, perfumes, defoamers, active ingredient preservatives and agents providing a retarding effect.  G. Granules according to one of claims X to 5, characterized in that they contain from 0.1 to 5% by weight, preferably from 0.2 to 1% by weight, of a wetting agent and a secondary dispersant.  7. Process for the preparation of deleterious granules according to one of claims X to 6, characterized by the fact that an intimate mixing, at the desired doses, of the active ingredient (s), the dispersing binder and the disintegrating hydrotrope is carried out. optionally other adjuvants, in the form of a homogeneous fine powder which may optionally subsequently be ground on a powder mill prior to rehomogenization, this powder then being introduced into a granulation apparatus, in particular a rotating plate granulator or a vessel equipped with agitators and clod-breaking systems, the granules finally being dried.  8. Process for the preparation of deleterious granules according to one of claims 1 to 6, characterized in that a powder is prepared containing a portion of the condensate and the salt of alkylbenzenesulfonic acid and adjuvants and sprayed on this powder an aqueous solution comprising the complement of these two products and adjuvants, the granules obtained being then dried.